CH634933A5 - PHOTOGRAPHIC PRODUCT CONTAINING COMPOUNDS RELEASING ACTIVE GROUPS BY OXYDO-REDUCTION. - Google Patents

Description

The present invention relates to photography and, in particular, to photographic products containing new compounds releasing, by redox, dyes or other photographically useful groups, depending on the development of silver halides.

French Patent No. 2154443 describes non-diffusible compounds which split by oxidation in an alkaline medium and release a dye, a dye precursor or another photographically useful and diffusible group. These compounds will be identified in the following description under the name of described compounds, or RDR compounds when the releasable group is a dye or a dye precursor. Useful compounds include weighted sulfonamido compounds, such as sulfonamidophenols and sulfonamidoanilines. The ballast group is a simple organic or polymeric radical, the size and molecular configuration of which are such that they make the compound non-diffusible during development by the alkaline treatment composition. The above patent mentions various specific ballast groups, usable with various ulfonamido compounds.

These various ballasted compounds of the sulfonamidophenol and sulfonamidoaniline type are very useful, but we have continued to search for compounds having a better ability to release a photographically useful group. In particular, it is desirable to find compounds which can provide, among other advantages, one or more of the following improvements:

- faster release of the photographically useful group in order to obtain better quality images in less time,

- higher quantity of photographically useful group, released per unit of developed silver halide,

- better ability to release the photographically useful group with a wider range of developer,

- ability to provide good quality color images under broader pH conditions,

- and improved sensitivity and better image discrimination.

It has been found that when the ballast group of a sulfonamido compound as described above is an N, N-disubstituted carbamoyl group, the compound unexpectedly exhibits an increased ability to release the photographically useful group and thus leads to the desired improvements listed above.

A subject of the present invention is therefore a photographic product comprising a support, at least one photosensitive emulsion layer with silver halides and a non-diffuse weighted compound releasing a photographically useful group by oxidation-reduction, characterized in that said compound contains a group carbamoyl N, N-disubstituted and has the formula:

G

J O R1

/ ^

z. ,; n2

NHSO -GFU

or

R1 and R2 independently represent an aliphatic or alicyclic group of 1 to 30 carbon atoms or an aromatic group of 6 to 30 carbon atoms,

s

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G represents a group —OR5 or —NHR6 where R5 is a hydrogen atom or a hydrolyzable group, and R6 is a hydrogen atom, an alkyl group of 1 to 22 carbon atoms or a group -SO2GPU,

Z represents the atoms necessary to complete a carbocyclic or heterocyclic group with 1,2 or 3 condensed rings containing from 5 to 7 atoms in each ring, the sulfonamido group being linked to the ring containing Z in a position such that it is conjugated with G, and

GPU is a photographically useful group. io

The hydrolyzable group which can represent R5 is, for example, an acyl group of 2 to 30 carbon atoms. The alkyl group capable of representing R6 is, for example, a methyl group,

ethyl, butyl, decyl or hexadecyl.

Typical Z-containing cycles include, for example, is benzene, naphthalene, anthracene, pyrazolone, pyridine, quinoline, pyrimidine, coumarin or indole.

Typical GPU groups include a dye, a dye precursor or a photographic reagent such as a development inhibitor, a development accelerator, a bleaching inhibitor, a bleaching accelerator, a developer, a silver halide solvent , a silver complexing agent, a fixer, a tone modifying agent, a tanning agent, a veiling agent, an anti-veil, a chemical (or spectral) sensitizer or a desensitizer. 25

According to a preferred embodiment, the photographic product according to the invention comprises a support and at least one photosensitive emulsion with silver halides, with which is associated a non-diffused weighted parasulfonamidophenol or a parasulfonamidoaniline to which is attached, via the sulfonamido group, a photographically useful group, releasable in an alkaline medium by oxidation and containing, in the meta position of the sulfonamido group, a N, N-substituted carbamoyl ballast group. The terms phenol and aniline include monocyclic and bicyclic compounds and therefore include naphthols as well as phenols and naphthylamines, as well as anilines.

Particularly advantageous parasulfonamidophenols and parasulfonamidoanilines can be represented by the formula:

(II)

NHS02GPU

where X represents the atoms necessary to complete a benzene or naphthalene ring, and R1, R2, G and GPU are as defined above.

In formulas I and II above, the substituents R1 and R2 in the N, N-disubstituted carbamoyl ballast group have a size and a configuration such that they render the compound non-diffusible during development in the alkaline treatment composition. Advantageously, R1 and R2 together together contain at least 8 carbon atoms, for example from 8 to 50 carbon atoms.

Advantageous groups R1 and R2 are alicyclic groups such as cycloalkyl of 4 to 22 carbon atoms (for example cyclohexyl, cyclodecyl or cyclooctadecyl), aliphatic groups such as straight or branched alkyl groups of 1 to 22 carbon atoms , including arylalkyl and aryloxyalkyl groups (e.g. methyl, butyl, dodecyl, benzyl or phenoxypropyl), and aromatic groups such as aryl groups of 6 to 22 carbon atoms, including alkaryl and alkoxyaryl groups (e.g. phenyl , naphthyl, methylphenyl and butoxyphenyl).

In a particularly advantageous embodiment, R1 and R2 are straight chain alkyl groups of 1 to 22 carbon atoms such as ethyl, pentyl, octyl, dodecyl, pentadecyl, octadecyl, or a 2,4-di- group t-pentylphenoxybutyl, and R1 and R2 together contain a total of at least 8 carbon atoms. In a very advantageous embodiment, R1 and R2 each represent the same straight chain alkyl group containing from 10 to 22 carbon atoms, such as decyl, dodecyl, pentadecyl or octadecyl.

In a particularly advantageous embodiment, G is a group —OR5 and R5 is a hydrogen atom.

In a particularly advantageous embodiment, GPU represents a dye or a dye precursor. These compounds are well known and include dyes such as azo dyes, azomethines, azopyrazolones, indoanilines, indophenols, anthraquinones, triarylmethanes, alizarines, merocyanines, nitro dyes, quinolines, cyanines, indigoids, phthalocyanines, dyes complexed by a metal, and dye precursors such as leuco derivatives or shifted dyes, that is to say of which the wavelength of the maximum absorption is displaced relative to the precursor.

These dyes or dye precursors may contain solubilizing groups - if desired - to improve transfer of the dye. The dye precursors can be transformed into dyes by known methods such as hydrolysis or oxidation either in the photosensitive product, in the treatment composition, or in the image-receiving layer, to form a visible dye. Advantageous dyes and dye precursors are described in U.S. Patent Nos. 3,880,658.3931144.3932380.3932381 and 3942987. Unless otherwise indicated, the term dye includes dye precursors, which are transformed into dye to form the final image.

Particularly advantageous compounds are parasulfonamidophenols which can be represented by the formula:

OH

X

(III)

NHS02-C0L

where X represents the atoms necessary to complete a benzenic or naphthalene nucleus,

COL is a dye or a dye precursor as defined above, and

R1 and R2 are straight chain alkyl groups of 1 to 30 carbon atoms and together contain a total of 8 to 50 carbon atoms.

Advantageous compounds are collated in the following table.

A. - Compounds releasing a blue-green dye corresponding to the general formula below:

011

60

f See next page)

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where the radicals R1, R2 and R3 have the following meanings:

Corcpoaä

r

"(CH.)

where R1 and R2 have the meanings defined below: „1

Compoafi XX

"c12h25" n ^

II

-0lzH25-n

-C12fl25-n

H

m

"Cl8H37" n

"C18H37" n

H

IV

"° 12" 25 ""

"C12H25 ~ n

CL

10

V

~ Cl8H37 ~ n

"Cl8l, 'S7" n

Cl

v:

-C2H5

- ^ ^ - OC18H37 "n

Cl

seen

-C5Hu-n

- (CH2) aO —Û y— ° 5Hxrc

Cl

15

IT"

? H3

SEEN!

"W"

"C18H37" "

-S02N (CHCH3) 2

IX

"CK.H29" n

- "" »V -0-Vu"

CL

20

OCH,

where R1 and R2 have the meanings defined below:

12 25 ~ n "^ vll

(cyclododecylc)

B. Compounds releasing a magenta dye corresponding to one of the following formulas 1,2 and 3:

Compoae

XXL

XXtT

(1)

-P

30

l4h29 "n

C. - Compounds releasing a yellow dye corresponding to one of the general formulas 1,2,3 and 4 below:

where the radicals R1 and R2 have the meanings defined below:

Compound XI

XIT XIII

XVI II XIX

- <c "2y-fycs" n-e

CjHii-c

~ ^ 3 ~ OC18H37'n

-CCH2) 40- <Q-C5H11-t

Vil "'

(cyclododecyl)

(i)

where R1 and R2 have the following meanings:

Compound

XXV

XXVt

60

(2)

(2)

where R1 and R2 have the following meanings:

Compoqd

(3)

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XXIV

ì ~ ^ 3 ~ "" h ~ hc3 ~

> r. i

Compound XXX

_R

-C, „H __- n

(4)

, - ^ r \ -s.

XXXV

Cotnpoaé XXXI

Examples of compounds which release blue-green indophenol dyes by redox include compounds which correspond to the following formulas:

oh 0

XXXII

—CN (C18H37) 2 XXXIII

0 Ti

Cl Cl

XXXVII

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An example of a compound releasing a blue-green leuco dye by redox is the compound XXXVII corresponding to the following formula:

OH

NHSO,

CONH

NH

"Cl

Cl '

OH

The photographic products according to the invention can be used in various processes in which it is desired to form (or improve an image), a distribution according to an image of a photographically useful group. The photographically useful group can be liberated in an image from the described compound. A distribution is thus obtained according to an image of a photographically useful compound, such as a dye, a dye precursor or a photographic reagent. A silver halide emulsion, containing such a compound and exposed according to an image, is treated with an alkaline treatment composition (having a pH, for example from 9 to 14), in the presence of a silver halide developer. . The silver halide develops with exposure and, at the same time, the developer oxidizes; the oxidized developer, by cross oxidation, oxidizes, directly or indirectly, the compound described, which, in its oxidized form, splits by releasing according to an image the photographically useful group. This distribution of the photographically useful compound can be used in various ways to form or enhance a photographic image.

The compounds described here are particularly useful in diffusion-transfer processes in which it is desired to release a dye or a dye precursor according to an image. However, certain embodiments of the invention relate to the distribution according to an image of diffuse photographic reagents, known in the art, such as those described in the patents of the United States of America Nos. 3227551, 3698898, 3379529 and 3364022. These reagents can be, for example, a silver complexing agent, a silver halide solvent, a tone modifier, a tanning agent, an anti-veil, a veiling agent, a chemical or spectral sensitizer, a desensitizer, a developer, inhibitor or accelerator of development, inhibitor or accelerator of bleaching. In other words, the radical —NHS02GPU in the above formula includes a group which, in association with a hydrogen atom, provides a photographic reagent by cleavage.

As an example of a product according to the invention, a product will be described in which compounds are used which release a dye to form color photographic images (RDR compounds).

Color photographic images can be obtained using a product according to the invention; it is treated in the manner described above to form a distribution according to an image of a dye or of a dye precursor which is diffusible as a function of the photographic exposure of the emulsion to silver halides. The image can be formed either by using the released diffusible dye, or by using the remaining unreacted RDR compound, or by using both. The released dye or diffusible dye precursor can be diffused into a receiving sheet to form a transfer image. You can also simply remove this dye without using it. Whether or not the diffusible dye is used to form an image, the RDR compound remaining in the form of image retained in the layer where it was initially introduced can be used. This involves removing the residual silver and silver halide by any known conventional method, such as a bleach bath followed by a fixing bath, a fixing bleach bath, etc. In the case where one uses not a dye, but a dye precursor, as a releasable group in the RDR compound, it is necessary to provide a step for transforming the precursor into the desired dye. One can also, once the diffusible dye initially formed and eliminated from the product, use the residual RDR compound to form an image by transfer by oxidizing the RDR compound, for example by cross oxidation, to give a second distribution of diffusible dye than can be transferred to an appropriate receiving sheet.

To obtain a color transfer photographic image, by means of a photosensitive element containing the compound described, a preferred method comprises:

a) the treatment of the photosensitive element, by means of an alkaline treatment composition and in the presence of a silver halide developing agent, which has the effect of developing each of the halide emulsion layers of exposed silver and, therefore, to form the oxidation product of the developing agent, which in turn oxidizes the RDR compound,

b) cleavage of the molecule of oxidized RDR compound, in an alkaline medium, in each of the layers and, consequently, the formation of a distribution of a diffusible dye, or of a precursor of diffusible dye, as a function of l exposure of each layer of silver halide, and c) the diffusion of at least part of these distributions of diffuse dyes or diffusible dye precursors, outside the layer where the RDR compound had been originally introduced.

The photosensitive member can be treated with an alkaline composition, to develop, or to initiate development in any way. A preferred technique for applying the treatment composition is to use a frangible capsule or sachet which contains the composition. In general, this composition which is used for the treatment of the photosensitive element, contains a developing agent for development, although one can be satisfied with a composition containing only an alkaline agent in solution, when the developing agent is itself incorporated into the photosensitive element; in this case, the alkaline solution serves to activate the incorporated developing agent.

A preferred photographic product according to the invention is a composite product which contains a silver halide developing agent and which comprises:

a) a photosensitive element as described above,

b) an alkaline treatment composition, and c) means for introducing the alkaline treatment composition into this product; these means consist, for example, of a frangible capsule which is adapted to be placed, during treatment, in such a way that a pressure force applied by means of pressing members causes its content to be injected inside said composite product.

The composite product may comprise an image-receiving layer arranged on a separate support adapted to be able to be applied in superposition on the photosensitive element after the exposure of the latter. Such image-receiving elements are described, for example, in United States Patent No. 3362819. When a frangible capsule is used, it is arranged relative to the photosensitive element and the receiving element images, so that a pressure force applied to this capsule by means of pressing devices such as those fitted with a camera for instant photography, causes the content of this capsule to be injected between the receiving element image and the layer of the photosensitive element which is furthest from the support of this element. After the treatment, the receiving element is separated from the photosensitive element.

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The dye image receiving layer can also be an integral part of the photographic product. A structure of this type is described in Canadian Patent No. 928560. According to such an embodiment, the support of the photosensitive element is transparent and it carries a dye image-receiving layer, a practically opaque and reflective layer of light, containing for example Ti02, then the layers of the photosensitive element. After exposure, a frangible capsule containing the alkaline composition for treatment and an opaque complementary sheet is applied in superposition. The pressing members with which the camera is equipped, cause the capsule to rupture and the treatment composition to spread over the photosensitive element, when the composite product is extracted from the camera. The treatment composition develops the silver halides exposed in each emulsion layer and dye images are formed based on this development; these dye images diffuse on the image-receiving layer where a positive image is obtained and at the place which can be examined through the transparent support on the image background provided by the reflective layer.

Another unitary composite product comprising a photosensitive element and a receiving element has been described in Canadian Patent No. 928559. According to this latter embodiment, the support of the transparent photosensitive element carries the image-receiving layer, a practically opaque and light-reflecting layer, the photosensitive element containing one or more photosensitive layers, as described below. above. A capsule containing an alkaline treatment composition and, in addition, an opacifying agent, is disposed in a position adjacent to both the layer furthest from the transparent support and to a transparent film disposed on this layer. This product is placed in a camera, in which it is exposed, through the transparent film, then it is passed between a pair of pressing members, with which the camera is equipped, at the time where we take him out of this camera. The pressing members cause the capsule to rupture and spread the treatment composition with the opacifying agent on the negative part of the product, so as to make it insensitive to light. The processing composition develops each layer of silver halides and dye images are formed as a result of the development; these images diffuse as far as the receiving layer where they form an image at the place which can be examined through the transparent support, with an image background provided by the opaque reflecting layer. Other unitary composite product structures in which the sulfonamido compounds can be used are described in US Pat. Nos. 34) 5644, 3415645, 3415646, 3647437 and 3635707.

The photographic product according to the present invention can be used to obtain positive images in one or more colors. In a three-color system, each layer of silver halide emulsion is associated with a dye image-forming substance, at least one of these substances being an RDR compound described; the spectral absorption of each substance is predominantly located in a region of the visible spectrum situated inside the zone of the visible spectrum which is that of the sensitivity of the emulsion to the associated silver halides; this means that the blue-sensitive emulsion layer is associated with a yellow dye-forming substance, the green-sensitive emulsion layer is associated with a magenta dye-forming substance and the red-sensitive emulsion is associated with a yellow dye-forming substance blue-green dye trainer. Silver halide emulsions which are not associated with a described RDR compound can be combined with another RDR compound or another dye image-forming substance. The dye-forming substance associated with each layer of silver halide emulsion can be incorporated either into the emulsion layer or into a layer adjacent to this emulsion layer.

The quantity of RDR compound that is used can be variable over a wide range depending on the nature of the RDR compound chosen and according to the results that it is desired to obtain. For example, it is possible to apply layers containing the RDR compounds in the form of dispersions in a film-forming and hydrophilic polymer of natural or synthetic origin, for example polyvinyl alcohol or gelatin, etc. This polymer must be able to be impregnated with an aqueous alkaline composition such as that used for the treatment. Advantageously, the ratio of the RDR compound to the polymer is between approximately 0.25 and 4. The compounds can be incorporated into the gelatin by known techniques, such as the use of an organic solvent immiscible with water and of high boiling point, or a water-miscible solvent with low boiling point.

Any silver halide developing agent can be used as long as it can give rise to cross-oxidation with the imaging compounds of the invention. This developing agent can be used in the photosensitive element and will be activated by the alkaline treatment composition. Among the examples of usable developing agents, there may be mentioned;

hydroquinone, aminophenols, such as N-methylamino-phenol, l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4 -hydroxymethyl-3-pyrazolidone, N, N-dimethyl-p-phenylenediamine, 3-methyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N, N-diethyl-p-phenylenediamine, N , N, N ', N'-tetramethyl-p-phenylenediamine, etc.

In this list, however, preferably the black and white developer agents are chosen, because they are less likely to form a haze on the dye image-receiving layer.

In a preferred embodiment, the silver halide developing agent oxidizes during development and reduces the silver halide to metallic silver. This oxidized developing agent gives rise to cross oxidation with the dye-forming compound. The product of this cross-oxidation then undergoes alkaline hydrolysis, which causes the release, depending on the image, of the diffusible dye or of the diffusible dye precursor; the diffuse substances thus formed diffuse as far as the receiving sheet where the dye image is formed. The diffusible substance can be transferred in the presence of the alkaline treatment solution either thanks to its own diffusing properties, or because its molecule carries one or more solubilizing groups.

When using the RDR compounds, a diffusible dye or a dye precursor is formed, depending on the development of the silver halides, using a silver halide developing agent, to form a direct negative or positive image. in the emulsion layers. If the emulsion that is used is a direct positive emulsion, for example an emulsion with an internal or solarized image which develops in unexposed areas, a positive image can be obtained on the dye image receiving layer. After the exposure of the composite product, the alkaline composition used for the treatment permeates the different layers and triggers the development of the unexposed silver halide layers therein, the developing agent present in the composite product develops each of the layers of emulsion in unexposed areas (since we are dealing with direct positive emulsions). This causes oxidation of the developer as shown in the unexposed areas of the direct positive emulsion layers. This oxidized developing agent gives rise to cross-oxidation with the dye-forming compounds and this dye-forming compound in the oxidized state undergoes a reaction, catalyzed by a base according to the preferred embodiment, which leads to the release of the dye. preformed or dye precursor according to the image and according to the exposure received by each of the emulsion layers. At least part of these diffusible images diffuses onto the image receiving layer to form a positive image of the original object. After being in contact with the alkaline treatment composition, an acid layer in the composite product lowers the pH of the product or of the receptor element to stop development and stabilize the image.

The internal image silver halide emulsions used in the embodiment described above are positive emulsions.

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direct tives which form predominantly latent images inside the silver halide grains, which distinguishes them from emulsions which form predominantly latent images on the surface of the grains. Such internal image emulsions are described in US Pat. Nos. 2592250, 3761276, 3935014 and 3957488. Internal image emulsions can be defined by the maximum density increase obtained by developing emulsions with internal type developers in relation to the maximum density obtained by developing these same emulsions with surface developers. The appropriate internal image emulsions are those which meet the following conventional photographic test. A sample of such an emulsion is applied in layer on a transparent support; exposing using a density scale for a period of between 0.01 s and 1 s, developing for 3 min at 20 ° C. in developer A below, which is an developer of internal type, and must thus obtain a maximum density which is at least equal to five times the maximum density obtained by exposing, likewise, an identical sample which is developed for 4 min at 20 ° C. in developer B below, which is a developer of superficial type. Preferably, the maximum density in developer A represents at least 0.5 density unit more than the value obtained with developer B.

Developer A

Hydroquinone 15 g

Monomethyl-p-aminophenol sulfate 15g

Anhydrous sodium sulfite 50 g

Potassium bromide 10g

Sodium hydroxide 25 g

Sodium thiosulfate 20 g Water q.s.p. 11

Developer B

p-Hydroxyphenylglycine 10 g

Sodium carbonate 100 g

Water q.s.p. 11

Internal image silver halide emulsions give direct positive images when treated in the presence of fogging agents or nucleating agents. Such emulsions are particularly useful in the embodiments described above.

The direct positive silver halide emulsions solari-es, useful for the embodiments described above, are well known emulsions; these emulsions were veiled either chemically by the use of reducing agents, or by means of radiation, to a point approximately corresponding to the maximum density on the inversion curve, as shown by Mees, in "The Theory of the Photography Process ”, Macmillan Co., New York, 1942, p. 261-297.

In certain embodiments of the invention, negative silver halide emulsions may be used comprising, for example, silver chloride, silver bromide, silver chloro-bromide, bromoiodide silver, silver chlorobromoiodide, or mixtures of these salts. The emulsions can be coarse or fine grain, and can be prepared by any known method.

In another embodiment, the inversion technique described in British Patent No. 904364, p. 29, lines 1-41. In this system, the RDR compounds associated with seeds of physical development are used in a nucleation layer adjacent to the photosensitive silver halide emulsion layer. The composite product contains a silver halide solvent, preferably in a frangible capsule with the alkaline treatment composition.

The different silver halide layers of a composite product for color photography according to the invention can be applied in the usual order, that is to say that, with respect to the exposure face, first, the silver halide emulsion layer sensitive to blue, then the green sensitive layer and the red sensitive layer. If desired, a layer of yellow dye - or a layer of Carey Lea silver - can be placed between the blue-sensitive layer and the green-sensitive layer, so as to absorb or filter out blue radiation that could be transmitted through the blue sensitive layer. If desired, the selectively sensitized emulsions can be arranged in a different order; for example, in relation to the exposure face, we can first find the blue sensitive layer, then the red sensitive layer and the green sensitive layer.

The frangible capsule usable according to the invention can be of the type described in the patents of the United States of America Nos 2543181, 2643886,2653732, 3724051, 3056492, 3056491 and 3152515. In general, such capsules are constituted by a rectangular sheet of a material, impermeable to air and fluids, which is folded longi-tudinally on itself so as to form two walls which are sealed to one another along their longitudinal and lateral edges; an enclosure is thus formed intended to contain the treatment solution.

Any substance can be used to form the image-receiving layer of a product according to the invention, provided that this substance allows the etching or fixing, by any other means, of dye images, the particular substance chosen depends,

of course, the dye that must be etched. If acid dyes are to be mor-danced, the image-receiving layer may contain basic polymeric mordants. The advantageous mordants are cationic mordants such as polymers comprising quaternary ammonium groups (that is to say for each positively charged nitrogen atom); in addition, these polymers are free of carboxyl groups. Cationic polymeric mordants of this type are described in US Patents Nos. 3709690, 3898088 and 3958995.

The stability of the transferred image can normally be increased by combining a neutralizing substance with the dye image-receiving element according to the invention. In general, this neutralizing substance makes it possible to reduce the pH of the layer carrying the image from an initial value of 13 or 14 to at least a value of 11 and, preferably, to a value of between 4 and 8, and this in a short time after impregnation. For example, it is possible to use acid polymers, as described in United States patent No. 3362819, or else solid acids or metal salts, for example zinc acetate, zinc sulfate, magnesium acetate, as described in US Patent No. 2584030. Such neutralizing substances lower the pH of the photographic product after development, so as to halt this development and decrease notably any transfer of dye subsequent to this development, which makes it possible to stabilize the image of dyes.

It is also possible to use a retarding layer or spacer layer which is placed on the neutralization layer and which serves to delay or control the decrease in pH as a function of the speed with which the alkali diffuses through this inert layer d 'spacing. The retarder layer can be effective in preventing large variations in reaction rate over a wide range of temperatures; this means that a premature decrease in pH can be prevented when the impregnation is carried out at temperatures above ambient temperature, for example at 30 ° C.

The alkaline treatment composition used according to the present invention is a conventional aqueous solution of an alkaline substance such as for example sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably having a pH greater than 11 , and advantageously containing a developer. This solution also preferably contains a viscosity-increasing agent, such as a high molecular weight polymer, for example an ether soluble in water and inert towards alkaline solutions such as hydroxyethylcellulose or the salts. of the alkali metal of carboxymethylcellulose, for example sodium carboxymethylcellulose.

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The practically opaque and reflective layer, permeable to alkaline solutions, used in certain embodiments of the composite product of the invention, can generally contain an opacifying agent in dispersion in a binder; the nature of this opacifying agent is indifferent provided that it makes it possible to obtain the desired properties.

The supports of the composite photographic products according to the invention can consist of any substance, provided that this substance does not alter the photographic properties of the composite product and provided, in addition, that these substances make it possible to obtain supports having good di-mentioned stability.

The silver halide emulsions which can be used according to the present invention are well known and are described, for example, in "Product Licensing Index", vol. 92, December 1971, publication 9232, p. 107, paragraph I “Typical emulsions”.

The following examples illustrate the invention.

Example 1:

Preparation of compound XXV:

Stage I:

9.2 g of azonaphthol c are dissolved in 200 ml of hot ethanol, then a solution of 6 g of sodium dithionite in 50 ml of water is added. The mixture is stirred vigorously and heated to reflux. After A h the dark solution becomes yellow and an oil appears on top of the solution. The mixture is stirred and heated for A hour, then cooled in an ice bath, with vigorous stirring. The light oil solidifies at around 5 ° C. The off-white product obtained is then collected and washed thoroughly with water. Recrystallized from n-hexane, and off-white crystals are obtained (PF: 55-56 C).

Step 4:

Compound XXV

35.3 g of di-n-dodecylamine are added to 26.5 g of ester a. The mixture is heated to about 120 ° C for 15 min. The temperature of the oil bath is increased to 180-190 ° C. and the phenol produced is removed by vacuum. The amber colored oil obtained is added, while it is still hot, to 400 ml of n-hexane. After cooling and standing, no precipitate appears. The solvent is removed in vacuo and an oil is obtained which gives a yellow precipitate by cooling in an acetone and dry ice bath. By crystallization from ethyl alcohol,

4 g of aminonaphthol d are dissolved in 50 ml of dry pyridine, then 2.8 g of sulfonyl chloride e are added, at 12 ° C., under a nitrogen atmosphere (the temperature increases to about 15 ° C. ). The mixture is stirred at 15 ° C for 2 h and at room temperature overnight. It is then added to 50 ml of concentrated hydrochloric acid and approximately 50 ml of ice water with vigorous stirring. The product is collected and washed thoroughly with water. Recrystallized twice from acetonitrile and 2.5 g of yellow-orange crystals are obtained (mp: 91-93 ° C).

Example 2:

Preparation of compound XXI:

15 g of naphthol b are dissolved in methanol, sodium hydroxide so and tetrahydrofuran; a solution of diazonium salt prepared with 3.7 g of p-anisidine, 30 ml of water, 9 ml of concentrated hydrochloric acid and 2.1 g of sodium nitrite dissolved in 30 ml is added to it at 0 ° C. of water. The mixture is stirred for 30 min at 5 ° C. A solution of 25 ml 55 of glacial acetic acid in 300 ml of ice water is then added, with vigorous stirring. The bright orange precipitate turns pale brown. The product is collected and washed thoroughly with water.

Step 3:

3 g of the aminonaphthol d prepared as in Example 1, steps 1 to 3 are dissolved in 50 ml of dry pyridine, then 2.6 g of sulfonyl chloride f are added at 15 ° C. under a nitrogen atmosphere. The mixture is stirred at 15 ° C for 2 h and at room temperature overnight. 50 ml of concentrated hydrochloric acid and 50 ml of water are then added with vigorous stirring. The magenta compound obtained is collected and washed thoroughly with water. Recrystallized from ethyl acetate and 2.1 g of product are obtained (PF: 185-188 "C).

Example 3:

Image formation retained by treatment in solution

Color photographic products having the structure shown below are prepared. The amounts of the components are given in g / m2 in parentheses, and the amounts of silver halides are given in silver.

Gelatin (1.08)

Negative silver halide emulsion (1.35)

Gelatin (2.70)

Blue-green, magenta or yellow RDR compound (see below) dissolved in half its mass of diethyllauramide Support: cellulose acetate.

634933

10

The blue-green, magenta and yellow RDR compounds are introduced into separate products and compared to control products comprising prior art RDR compounds having the same blue-green, magenta and yellow coloring groups. The formula and the quantity (g / m2) of the RDR compounds introduced into each product are as follows:

Blue-green RDR compound

HHSO,

NO,

lO-NH

OH

Product A (control)

Compound 12 of U.S. Patent No. 3,942,987 (0.92)

Product B (invention) Compound II (0.97) R1 and R2 = C12H25-n

RDR magenta compound

OH

HHSO,

Product C (control)

Compound 6 of U.S. Patent No. 3,932,380

Product D (invention) Compound XII (1,13) R1 and R2 = C12H25-n

Yellow RDR compound

OH

OH

Product E (control)

Compound 1 of United States Patent No. 3923510 (1.30)

Product F (invention)

Compound XXX (1.30)

R1 and R2 = C12H25-n

Samples of each product are exposed on a sensitometric scale and treated by dipping them in the following developer:

NaOH 2.2 g

Na3POI4 38.8 g

Na2S03 4.85 g

KBr 10.0g

5-Methylbenzotriazole 0.1 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.3 g

Water q.s.p. 11 pH adjusted to 11.5

■ Products A and B are developed at 24 ° C for 8 min, products C and D at 24 ° C for 6 min and products E and F at 24 ° C for 3 min. All samples are then washed for 1 min, soaked in a bleach-fix bath for 2 min, washed for 2 min and soaked in a buffer solution, pH 7, for 1 min. A color image of the sensitometric scale is obtained.

The results are evaluated by drawing the curves giving the densities of the images as a function of the exposure. We obtain the curves of fig. 1,2 and 3.

It is observed that the images produced with the RDR compounds described in the invention exhibit a significant increase in the photographic sensitivity and a notable decrease in the minimum densities. In addition, to evaluate the yellow veil, the density in blue light is measured in the minimum density ranges of the curves of FIGS. 1 and 2; there are 0.16 for product A against 0.09 for product B, and 0.21 for product C against 0.12 for product D.

Example 4:

To compare the results given by the RDR compounds described in the invention, at various treatment pHs, compared with similar compounds of the prior art, two color photographic products are prepared similar to the products C and D of Example 3 and having the following structures:

Product G (control)

Gelatin (1.08)

Negative silver halide emulsion (1.08)

Gelatin (2.16)

Compound 6 of U.S. Patent No. 3,932,380 (1.35) dissolved in diethyllauramide (0.68)

Support: cellulose acetate Product H (invention)

Gelatin (1.08)

Negative silver halide emulsion (1.35)

Gelatin (2.16)

Compound XII (1.08) dissolved in diethyllauramide (0.54)

Support: cellulose acetate

Samples of each product are exposed on a sensitometric scale and treated by dipping separate samples in various developers differing only in pH for 12 min and 6 min at 38 ° C. The processing steps are as follows:

Development 1 lA or 6 min

Wash 1 min

Whitening-fixing 2 min

Wash 1 min

Stabilization (pH 7.0 buffer) 1 min

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634,933

Developer:

Potassium bromide 10.0 g

5-Methylbenzotriazole 0.1 g 4-Hydroxymethyl-4-methyl-l -

phenyl-3-pyrazolidone 0.3 g

Potassium phosphate 38.8 g

Water q.s.p. 11

pH adjusted with KOH (see table I)

The sensitometric results are determined by plotting curve 5 giving the densities of the images as a function of the exposure. These results are collated in Table I.

Table I Development: 1.5 min

blue

^ min green

^ max green

Max money dev. *

pH

Witness

Compound XII

Witness

Compound XII

Witness

Compound XII

Witness

Compound XII

13.7 12.5 12.0 11.5 11.0 '10.5 10.0

0.34

0.33 0.39 0.53 0.71 0.91

0.17 0.15 0.13 0.18 0.32 0.47 0.59

0.30

0.87 1.33 2.32 3.28 4.20

0.18 0.20 0.26 0.63 1.52 2.26 2.74

3.6

3.9 4.0 4.0 3.9 4.2

1.8 **

3.3 3.2

3.4

3.4

3.5 3.5

0.51

0.48 0.44 0.30 0.14 0.05

0.41 0.37 0.33 0.32 0.24 0.22 0.18

Development: 6.0 min

^ min blue

^ min green

"-'max green

Max money dev. *

pH

Witness

Compound XII

Witness

Compound XII

Witness

Compound XII

Witness

Compound XII

13.7 12.5 12.0 11.5 11.0 10.5 10.0

0.33

0.28 0.30 0.34 0.56 0.85

0.20 0.17 0.15 0.14 0.17 0.32 0.49

0.24

0.64 0.82 1.28 2.32 3.83

0.19 0.18 0.18 0.22 0.50 1.45 2.40

1.6

3.7

3.8

3.9 4.0 4.4

0.20 **

2.1

3.1

3.3

3.4

3.4

3.5

0.68

0.69 0.69 0.60 0.37 0.18

0.65 0.57 0.52 0.53 0.50 0.38 0.31

* The maximum silver developed is the silver analyzed in g / m2 obtained in the exposure ranges of each sample.

** The reduced maximum dye density is the result of the development of the haze, i.e. the release of dye in unexposed areas.

The data in Table I show that the following improvements are made by the invention:

1) A lower minimum green density in the products according to the invention, compared to the control. This shows a more efficient release of the dye per unit of silver developed. so

2) A lower blue minimum density in the products according to the invention, compared to the control. It is assumed that this is due to a lower amount of yellow haze coming from the residual weighted carrier group, as well as a lower amount of residual dye.

3) The discrimination of the image is improved, in particular in relatively low pH conditions, as shown by the greater difference between the minimum and maximum densities in the green for products according to the invention, compared to the control. .

4) Faster development. This is suggested by the release of dye from unexposed areas under high pH conditions, which indicates that the development times used in this example are too long for the product according to the invention.

Example 5: 65

Color image transfer:

A control product is prepared containing RDR compounds of the sulfonamidonaphthol type of the prior art, by applying the following layers, suitably tanned, in the order given, on a transparent support of polyethylene terephthalate. The amounts of the components are given in brackets in g / m2 and the amounts of silver halides are given in silver.

Product I (control)

1) Image-receiving layer formed from a copolymer of styrene, N-benzyl-N sulfate, N-dimethyl-N-vinylbenzylammonium and biting di-vinylbenzene (2.16) and gelatin (2.16) .

2) Reflective layer of titanium dioxide (21.60) and gelatin (3.24).

3) Opaque layer of carbon black (2.30) and gelatin (1.73).

4) Compound A forming blue-green dye (0.59) dissolved in diethyllauramide (0.30) and dispersed in gelatin (1.08).

5) Direct positive silver bromide emulsion sensitive to red (1.35), gelatin (1.35), 5-sec.-octadecylhydroquinone-2-sulfonic acid (16 g / mol of silver), l- [ 4- (2-formylhydrazino) phenyl] -3-phenylthio-urea (3.5 mg / mol silver), l-acetyl-2- {p- [5-amino-2- (2,4-di- t-pentylphenoxy) benzamido] phenyl} hydrazine (85 mg / mol silver).

6) Gelatin interlayer (1.62) and 2.5-sec.-dodecylhydro-quinone (1.30).

7) Compound B forming magenta dye (0.54) dissolved

634933

12

in diethyllauramide (0.27) and dispersed in gelatin (1.22).

8) Direct positive silver bromide emulsion sensitive to green (1.35), gelatin (1.35), 5-sec.-octadecylhydroquinone-2-sulfonic acid (16 g / mol of silver), l- [ 4- (2-formylhydrazino) phenyl] -3-phenylthio-urea (2.5 mg / mol silver); 1-acetyl-2- {p- [5-amino-2- (2,4-di-t-pentylphenoxy) benzamido] phenyl} hydrazine (70 mg / mol silver).

9J Gelatin interlayer (1.62) and 2.5-sec.-dodecylhydro-quinone (1.30).

10) Compound C forming yellow dye (0.65) dissolved in diethyllauramide (0.32) and dispersed in gelatin (1.46).

11) Direct positive silver bromide emulsion sensitive to blue (1.24), gelatin (1.24), 5-sec.-octadecylhydroquinone-2-sulfonic acid (16 g / mol of silver), l- [ 4- (2-formylhydrazino) phenyl] -3-phenylthio-urea (3.3 mg / mol silver), l-acetyl-2- {p- [5-amino-2- (2,4-di- t-pentyIphenoxy) benzamido] phenyl} -hydrazine (80 mg / mol silver).

12) Gelatin overlay (0.89).

Compound A:

OH

NHSO,

N-N-

Cl

OH

Compound B:

Oh

NHSO.

N = N

Oh

Compound C:

Oh

'5 11

NHSO,

Cl

OH

"^ 5y-CNHCCH,

CN

A second product is prepared as above, except that the blue-green, magenta and yellow RDR compounds are replaced by compounds described in the invention in lower quantities; these compounds contain the same coloring groups as the control compounds. Also less emulsion and gelatin and more nucleating agents are used. The structure of the product is as follows:

Product J (invention)

1-3) Same composition as the witness.

4) Compound IV forming blue-green dye (0.32) dissolved in diethyllauramide (0.16) and dispersed in gelatin (1.08).

5) Direct positive silver bromide emulsion sensitive to red (0.92), gelatin (0.92) and other constituents identical to the control.

6) Interlayer identical to the witness.

7) Compound XII forming a magenta dye (0.32) dissolved in diethyllauramide (0.16) and dispersed in gelatin (1.22).

8) Direct positive silver bromide emulsion sensitive to green (0.92), gelatin (0.92) and other constituents identical to the control.

9) Interlayer identical to the witness.

10) Compound XXIX forming yellow dye (0.43), dissolved in diethyllauramide (0.22) and dispersed in gelatin (1.46).

11) Direct positive bromide silver emulsion sensitive to blue (0.92), gelatin (0.92) and other constituents identical to the control.

12) Same overlay as the witness.

Samples of the photosensitive products thus prepared are exposed on a color sensitometric scale. The exposed samples are then treated at 22 ° C. by breaking a capsule containing a viscous treatment composition between the photosensitive product and a transparent complementary sheet.

The treatment composition contains the following constituents:

Potassium hydroxide 48.8 g

Sodium sulphite 1.0 g

5-Methylbenzotriazole 3.8 g 4-hydroxymethyl-4-methyl-1-phenyl-

3-pyrazolidone 12.0 g t-Butylhydroquinone 0.3 g

Potassium fluoride 10.0 g

Carbon dispersion (carbon) 172.0 g

Carboxymethylcellulose 44.0 g

Water q.s.p. 11

The complementary sheet is formed from a transparent support of polyethylene terephthalate to which is applied:

1) A layer of polyacrylic acid (189 meq / m2).

2) A retardant layer formed of 2.16 g / m2 of a mixture of 89% acetylated cellulose acetate at 40% and 11% of a copolymer of styrene and maleic anhydride (hydrolysis at approximately 50% ).

3) A second retarding layer formed of 2.16 g / m2 of a latex consisting of a copolymer of acrylonitrile, vinylidene chloride and acrylic acid.

One obtains images transferred in color in the receiving layer, images which one sees through the transparent support. We draw the characteristic curves (density as a function of exposure), which are given in figs. 4 and 5.

It is observed that practically equal densities are obtained in the two products, although the ori has used in the product according to the invention significantly less amounts of constituents, such as silver halide, gelatin and RDR compounds.

In addition, a significant increase in sensitivity is observed in the product according to the invention, in particular in the layer sensitive to green.

Example 6:

Photographic products are prepared by applying to a support of polyethylene terephthalate a photosensitive layer consisting of a negative silver halide emulsion (1.08 g / m2), gelatin (3.24 g / m2) and d one of the magenta dye-forming RDR compounds, identified below (1.08 x 10-3 mol / m2) dissolved in an equal mass of diethyllauramide and dispersed in gelatin.

Separate samples of each product are exposed on an sensitometric scale and treated at room temperature by juxtaposing them with an image-receiving layer and spreading a viscous treatment composition between the product and this receiving layer.

The image-receiving layers are formed of a transparent support of polyethylene terephthalate on which is applied a layer of gelatin (2.2 g / m2) and of copolymer of divinyl-benzene, styrene and chloride of N- benzyl-N, N-dimethyl-N-vinylbenzylammonium (2.29 g / m2).

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634933

The viscous treatment composition contains the following compounds:

Potassium hydroxide 60 g

4-Hydroxymethyl-4-methyl-1 -phenyl-

3-pyrazolidone 2.0 g

Potassium bromide 20 g

5-Methylbenzotriazole 1.0 g Carboxymethylcellulose 51 g Water q.s.p. 11

The two parts are separated after 2 min. The initially photosensitive parts are treated in a bleaching-fixing bath, washed, treated in a pH 10 buffer and dried. The receiving layers are washed and dried. In each case, a well defined negative dye image is obtained, transferred to the receiving layer, and a positive image retained in the initially photosensitive part.

The minimum and maximum densities are measured by transmission of each sample. These densities are collated in Table II.

Identification of compounds

Magenta dye-forming compounds

Compound

R1

R2

XIV

-c2h5

"<(3-0018h37-n

XIX

- @ * 2) u

(cyclododecyl)

XIII

-ch3

18 37

Table II

Compound

Selected image

Image transferred

^ max.

®min.

^ max.

'-'min.

XIV XIII XIX

2.95 3.02 2.84

0.20 0.25 0.12

2.68 3.00 3.04

0.08 0.12 0.20

The compounds all release the same magenta dye.

Example 7;

Photographic products are prepared by applying to a support of polyethylene terephthalate a photosensitive layer consisting of a negative silver halide emulsion (1.08 g / m2), gelatin (3.24 g / m2) and d 'one of the RDR blue-green dye-forming compounds identified below (7.56 x 10 -4 mol / m2) dissolved in an equal weight of ethyl 4-cyclohexanedimethanoldi-2-hexanoate.

Separate samples of each product are exposed on an sensitometric scale, and treated at room temperature by juxtaposing them with an image-receiving layer and spreading a viscous treatment composition between the product and this receiving layer.

The image-receiving layers are formed of a transparent support of polyethylene terephthalate on which is applied a layer of gelatin (2.29 g / m2) and of copolymer of divinyl-benzene, styrene and chloride of N- benzyl-N, N-dimethyl-N-vinylbenzylammonium (2.29 g / m2).

The viscous treatment composition contains the following compounds:

Potassium hydroxide 60 g

4-Hydroxymethyl-4-methyl-1-phenyl-

3-pyrazolidone 2.0 g

Potassium bromide 20 g

5-Methylbenzotriazole 1.0 g Carboxymethylcellulose 51 g Water q.s.p. 11

The two parts are separated after 2 min. The initially photosensitive parts are treated in a bleaching-fixing bath, washed, treated in a pH 10 buffer and dried. The receiving layers are washed and dried. In each case, a well-defined negative dye image is transferred to the receiving layer, and a positive dye image retained in the initially photosensitive portion is obtained.

The minimum and maximum densities are measured by transmission of each sample. These densities are given in Table III.

Blue-green dye-forming compounds

OH

Compound

r1

r2

vi

-c2h5

-q> - °° 18.37-n vii

- cshn-n

- <cv4 ° - <f y ~ C5Hu-t:

c5hu-t

New

dial xxxviii

—Ci2H25-n

- (gçVu

(cyclododecyl)

Table III

Compound

Selected image

Image transferred

^ max.

^ min.

^ max.

^ min.

VI

VII XXXVIII

3.26 3.24 3.04

0.28 0.24 0.30

3.38 3.28 2.86

0.10 0.08 0.15

The compounds all release the same blue-green dye.

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5 sheets of drawings

Claims (8)

634933 1. Photographic product comprising a support, at least one emulsion layer photosensitive to silver halides and a weighted, non-diffusible compound, capable of releasing a photographic group. only useful by redox, characterized in that said compound contains an N, N-disubstituted carbamoyl ballast group and has the following formula: G s / r1 Z N, C-N v \ 2 NHS02-GPU or R1 and R2 independently represent an aliphatic or alicyclic group of 1 to 30 carbon atoms, or an aromatic group of 6 to 30 carbon atoms, G represents a group —OR5 or - NHR6, where R5 is a hydrogen atom or a hydrolyzable group, and R6 is a hydrogen atom, an alkyl group of 1 to 22 carbon atoms, or a group -so2-gpu, Z represents the atoms necessary to complete a carbocyclic or heterocyclic group with 1,2 or 3 condensed nuclei containing from 5 to 7 atoms in each ring, the sulfonamido group (NHS02) —GPU being linked to Z in a position as it is conjugated with G, and GPU is a photographically useful group. '\ 2 x V T NHS02 "GPU where X represents the atoms necessary to complete a benzenic or naphthalene nucleus. 2. Product according to claim 1, characterized in that the weighted, non-diffusible compound is a p-sulfonamidophenol or a p-sulfonamidoaniline to which is linked, via a sulfonamido group, a photographically useful group which is releasable by oxidation in alkaline medium and in which the N, N-disubstituted carba-moyl ballast group is in the meta position of the sulfonamido group. 2 3. Product according to one of claims 1 or 2, characterized in that the weighted, non-diffusible compound, corresponds to the formula: G I 0 R1 4. Product according to one of claims 1 to 3, characterized in that the photographically useful group is a dye or a dye precursor. 5. Product according to one of claims 1 to 4, characterized in that, in the formulas, R1 and R2 are straight chain alkyl groups containing a total of 8 to 50 carbon atoms, G is an —OH group, and GPU is a dye or a dye precursor. 6. Product according to claim 3, characterized in that, in the formula, X represents the atoms necessary to complete a naphthalene nucleus. 7. Product according to one of claims 1 to 6, characterized in that the non-diffusible weighted compound is introduced into a layer of silver halide emulsion, or into a layer adjacent to a layer of halide emulsion silver. 8. Product according to one of claims 1 to 7, characterized in that it contains at least one layer of direct positive silver halide emulsion.